Diastereoselective and Enantioselective Hydrophosphinylations of Conjugated Enynes, Allenes and Dienes via Synergistic Pd/Co Catalysis DOI

Minhao Tang,

Zhen‐Yu Yang, Aijun Han

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 137(1)

Published: Sept. 10, 2024

Abstract Different from the reported work focusing on construction of single P ‐ or C ‐stereocenter via hydrophosphinylation unsaturated carbon bonds, highly diastereo‐ and enantioselective reaction allenes, conjugated enynes 1,3‐dienes is achieved a designed Pd/Co dual catalysis newly modified masked phosphinylating reagent. A series allyl motifs bearing both tertiary are prepared in generally good yields, >20 : 1 dr, rr 99 % ee. The unprecedented 1,3‐enynes established to generate skeletons containing nonadjacent chiral axis. first stereodivergent also developed achieve all four ‐containing stereoisomers. present protocol features use only 3‐minutes time 0.1 catalyst, with observation up 730 TON. set mechanistic studies reveal necessity roles two metal catalysts corroborate synergistic process.

Language: Английский

NiII-Catalyzed Enantioselective Anti-Markovnikov Hydrophosphination of Unactivated Alkynes DOI

Wei-Han Wang,

Yue Wu,

Peng-Jia Qi

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(10), P. 6994 - 7001

Published: May 9, 2023

A mechanism-inspired, reaction mode-controlled enantio- and regioselective anti-Markovnikov hydrophosphination of unactivated alkynes was accomplished by NiII catalysis. Alkenyl phosphine products could be obtained with high regio- enantioselectivity easily derivatized to structurally diverse chiral compounds. Mechanistic studies on both Ni0-catalyzed Markovnikov addition NiII-catalyzed have been carried out combining experimental computational methods. In the Ni0 system, an allyl nickel complex as catalyst resting state whose structure unambiguously determined single-crystal XRD analysis. sequential hydrometallation, ligand exchange, reductive elimination mechanism elucidated corroboratively DFT calculations. cationic secondary serves active catalyst. migratory insertion protonation sequence operative accomplish hydrophosphination.

Language: Английский

Citations

26
Copper‐Phosphido Catalysis: Enantioselective Addition of Phosphines to Cyclopropenes** DOI

Brian S. Daniels,

Xintong Hou,

Stephanie A. Corio

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(36)

Published: June 19, 2023

We describe a copper catalyst that promotes the addition of phosphines to cyclopropenes at ambient temperature. A range cyclopropylphosphines bearing different steric and electronic properties can now be accessed in high yields enantioselectivities. Enrichment phosphorus stereocenters is also demonstrated via Dynamic Kinetic Asymmetric Transformation (DyKAT) process. combined experimental theoretical mechanistic study supports an elementary step featuring insertion Cu

Language: Английский

Citations

25
Rare Earths—The Answer to Everything DOI Creative Commons

Thomas Behrsing,

Victoria L. Blair, Florian Jaroschik

et al.

Molecules, Journal Year: 2024, Volume and Issue: 29(3), P. 688 - 688

Published: Feb. 1, 2024

Rare earths, scandium, yttrium, and the fifteen lanthanoids from lanthanum to lutetium, are classified as critical metals because of their ubiquity in daily life. They present magnets cars, especially electric cars; green electricity generating systems computers; steel manufacturing; glass light emission materials for safety lighting lasers; exhaust catalysts supports; artificial rubber production; agriculture animal husbandry; health cancer diagnosis treatment; a variety electronic products essential modern living. have potential replace toxic chromates corrosion inhibition, magnetic refrigeration, new materials, role may expand. This review examines sustainability, environment, recycling, crop production, feedstocks, catalysis, health, well considering future uses.

Language: Английский

Citations

10
Recent advances in hydrofunctionalisation of cyclopropenes via carbon–heteroatom bond formation DOI
Jorge García‐Lacuna, Gema Domı́nguez, Ángel Manu Martínez

et al.

Organic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review highlights recent advances in the hydrofunctionalisation of cyclopropenes through formation carbon–heteroatom bonds for synthesis polysubstituted cyclopropanes.

Language: Английский

Citations

1
Copper(I)‐Catalyzed Asymmetric Hydrophosphination of 3,3‐Disubstituted Cyclopropenes DOI
Shuai Zhang, Jiang Nan,

Jun‐Zhao Xiao

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(40)

Published: Aug. 18, 2023

Herein, a copper(I)-catalyzed asymmetric hydrophosphination of 3,3-disubstituted cyclopropenes is reported. It provides series phosphine derivatives in high to excellent diastereo- and enantioselectivities. The methodology enjoys broad substrate scope on both diarylphosphines. stereoselectivity attributed the stability Cu(I)-(R,R)-QUINOXP* complex presence stoichiometric HPPh2 produced phosphines, high-performance induction complex. Finally, method used for synthesis new chiral phosphine-olefin compounds built cyclopropane skeleton, one which serves as wonderful ligand Rh-catalyzed conjugate addition phenylboronic acid various α,β-unsaturated compounds.

Language: Английский

Citations

23
Recent advances in catalytic pnictogen bond forming reactionsviadehydrocoupling and hydrofunctionalization DOI
Matthew B. Reuter, Dennis M. Seth, Diego R. Javier‐Jiménez

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(10), P. 1258 - 1273

Published: Jan. 1, 2023

An examination of several catalytic reactions among the group 15 elements is presented. The connections between chemistry pnictogens can sometimes be challenging, but aspects metal-pnictogen reactivity are key. connecting comes from metal-catalyzed transformations such as dehydrocoupling and hydrofunctionalization. Pivotal mechanistic insights E-N heterodehydrocoupling have informed development highly active catalysts for these reactions. Metal-amido nucleophilicity often at core this reactivity, which diverges phosphine arsine dehydrocoupling. Nucleophilicity connects to earliest understanding hydrophosphination catalysis, more recent leveraging enhanced insertion activity through photolysis. This photocatalysis extends hydroarsination, may also metal-arsenido than anticipated. However, arsinidene foreshadowed related phosphinidene by years. shows potential greater influence individual discoveries leverage new advances elements, it suggests that heavier on what possible with lighter elements.

Language: Английский

Citations

12
Copper‐Catalyzed Enantioselective Hydrophosphorylation of Unactivated Alkynes DOI Open Access

Jie Kang,

Kang Ding,

Si‐Mu Ren

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 5, 2024

P-stereogenic phosphorus compounds are essential across various fields, yet their synthesis via enantioselective P-C bond formation remains both challenging and underdeveloped. We report the first copper-catalyzed hydrophosphorylation of alkynes, facilitated by a newly designed chiral 1,2-diamine ligand. Unlike previous methods that rely on kinetic resolution with less than 50 % conversion, our approach employs distinct dynamic asymmetric transformation mechanism, achieving complete conversion racemic starting materials. This reaction is compatible broad range aromatic aliphatic terminal producing products high yields (up to 95 %), exclusive cis selectivity, exceptional regio- enantioselectivity (>20 : 1 r.r. up 96 ee). The resulting were further transformed into diverse array enantioenriched scaffolds. Preliminary mechanistic studies conducted elucidate details.

Language: Английский

Citations

4
Copper(I)-catalyzed asymmetric hydrophosphination of alkenyl azaarenes DOI Creative Commons

Jun‐Zhao Xiao,

Wen‐Jun Yue,

Jiang Nan

et al.

Green Synthesis and Catalysis, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Language: Английский

Citations

0
Three-Coordinate Monomeric Phosphido Complexes of Ni(II) DOI
Abolghasem Bakhoda

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 20, 2025

This paper reports the synthesis of first series terminal phosphido Ni(II) complexes supported by β-diketiminato ligand [iPrNN] (where iPrNN = 2,4-bis(2,6-diisopropylphenylimido)pentyl). Neutral mononuclear [iPrNN]Ni–PPh2 (2) and [iPrNN]Ni–PAd2 (3) were obtained from reaction [iPrNN]NiBr2Li(thf)2 (1) with R2PM (R Ph, 1-adamantyl (Ad); M Li, K) phosphide reagents. The structures synthesized compounds determined single-crystal X-ray diffraction, which revealed that Ni center in these is three-coordinate an almost planar geometry when R Ph a pyramidal Ad. reactivity was also studied range bond forming reactions, including P–C P–P bonds.

Language: Английский

Citations

0
C−P Bond Formation by Nickel or Cobalt Catalyzed Coupling Reactions DOI Open Access
Anju Modi, Corinne Gosmini, Audrey Auffrant

et al.

Chemistry - An Asian Journal, Journal Year: 2025, Volume and Issue: unknown

Published: March 12, 2025

Abstract This review discloses nickel‐ and cobalt‐catalyzed coupling reactions that allow C−P bond formation. Activation of C−halide bonds to form phosphonium, pentavalent phosphorus, or trivalent phosphorous compounds has been reported with both metals. However, the conversion C−O ((activated) ethers, carbonates, acetates) into ones only described Ni. Similarly, there are more examples C−Y (Y=C, S, N, B) activations catalyzed by Ni than Co. Nevertheless, cross‐dehydrogenative reaction between a P−H reagent C−H often cobalt nickel. In addition, for metals, electrolytic photocatalytic processes have shown produce variety containing molecules. aims provide an overview potential metals formation highlight remaining challenges.

Language: Английский

Citations

0